Acrylic polymer monolithics

Methacrylate monoliths have been fabricated by free radical polymerization of a number of different methacrylate monomers and cross-linkers [107,141-163], whose combination allowed the creation of monolithic columns with different chemical properties (RP [149-154], HIC [158], and HILIC [163]) and functionalities (lEX [141-153,161,162], IMAC [143], and bioreactors [159,160]). Unlike the fabrication of styrene monoliths, the copolymerization of methacrylate building blocks can be accomplished by thermal [141-148], photochemical [149-151,155,156], as well as chemical [154] initiation. In addition to HPLC, monolithic methacrylate supports have been subjected to numerous CEC applications [146-148,151]. Acrylate monoliths have been prepared by free radical polymerization of various acrylate monomers and cross-linkers [164-172]. Comparable to monolithic methacrylate supports, chemical [170], photochemical [164,169], as well as thermal [165-168,171,172] initiation techniques have been employed for fabrication. The application of acrylate polymer columns, however, is more focused on CEC than HPLC. 

Fintschenko, Y., Choi, W.Y., Ngola, S.M., Chip electrochromatography of polycyclic aromatic hydrocarbons on an acrylate-based UV-initiated porous polymer monolith, Fres. J. Anal. Chem. 2001, 371(2), 174-181. 

Polymer monoliths are prepared by in situ polymerization of monomers such as styrene, acrylate, methacrylate, acrylamide, or cyclic compounds and have been reviewed thoroughly [19]. The selectivity of the monolithic column can be changed by incorporation of functional monomers during the polymerization. A... 

An MIP adsorbent is prepared for the extraction of 7-diethylamino-4-methyl-coumarin (Fig. 3). The print molecule, 7-diethylamino-4-methylcoumarin (4 mmol, 0.925 g), a functional monomer, 2-(trifluoromethyl) acrylic acid (12 mmol, 1.681 g), a cross-linking monomer, ethylene glycol dimethacrylate (60 mmol, 11.893 g) and a polymerization initiator, 2,2 -azobis(2,4-dimethylvaleronitrile) (0.140 g) are dissolved in anhydrous toluene (18 mL) in a 50-mL borosilicate PYREX tube.The solution is briefly purged with dry nitrogen for 5 min and sealed with a screw cap. The PYREX tube is transferred to a water bath preset at 45°C and maintained for 16 h. After polymerization, the polymer monolith is taken from the PYREX tube and fractured. This is further ground with a mechanical mortar (Retsch, Haan, ERG) and wet-sieved with 5% ethanol (v/v), and subjected to repetitive sedimentation in... 

A polymeric monolith is a continuous porous polymeric rod made from a mixture of an initiator, monomers (including a cross-linking monomer), and a porogen (pore-forming solvent) that are polymerized in situ in a column. Tuning of the porous properties is typically achieved with a mixture of solvents such as toluene, THF, or decanol. The rationale for choosing an initiator depends on the mode of initiation and on solubility aspects. A common initiator is 2,2-azo-bis-isobutyronitrile (AIBN). Most polymerizations are radical polymerizations, activating radical formation either thermally [54] or with UV radiation [55]. Common monomers used in the preparation of polymer monoliths are styrene, (meth)acrylate, and acrylamide-based materials. The formation of the monolith... 

Table 1.1 gives a comprehensive, albeit fragmentary, snmmary of investigated organic monolithic polymer systems (based on all different kinds of styrene, acrylate, methacrylate, (meth)acrylam-ide building blocks, as well as mixtnres thereof) together with their preparation conditions and ntilization as stationary phase. 

PNIPAM and its copolymers are not the only options for thermoresponsive stationary HPLC phases. Poly(acrylates) and poly(methacrylates) bearing OEG groups in the side chains are known as thermoresponsive polymers that offer some advantages over PNIPAM [40]. Such polymers were recently employed for the modification of silica monoliths, which then served as stationary phase in the HPLC separation of steroids [193], Unsurprisingly, the results were qualitatively similar to those obtained for PNIPAM-based systems, but the separation of relatively hydrophilic steroids was superior. 

Separations of complex steroid mixtures were achieved recently by Que et al. [76] using both isocratic and gradient elution. Mass spectrometric detection gave femto-mole detection limits while laser-induced fluorescence of dansylated ketosteroids ranged in attomole levels (Fig. 10.16). Monolithic column packings were used with a 35 cm (25 cm packed bed) x 100 pm i.d. capillary packed with a polymer prepared from 5% T (total monomer concentration), 60% C (total crosslinker concentration), 3% polyethylene glycol, 10% vinylsulfonic acid and 15% lauryl acrylate. Details of the monolithic column preparation can be found in refs. 36,76, and 193. Similar monolithic columns can be used for the separation of bile acids [194],... 

The monoliths are prepared both from organic (mainly based not only on polystyrene, acrylamides, acrylates, or methacrylates but also on imprinted polymers) and inorganic materials (based on sUica, zirconia, titania, or aluminium oxide) as continuous... 

The flow control elements or valves developed in Sandia were plugs of nonporous monolithic polymer prepared from fluorinated acrylates via UV-initiated polymerization directly in one of the channels. The reason for using the fluorinated monomers is to manage the surface energy, decrease their friction in channel, enable actuation at a low pressure, as well as to avoid both swelling and shrinking in solvents typically used in reversed-phase separations such as water and acetonitrile. The friction could be further decreased by modification of the valve channel with fluorinated alkylsilane. However, the latter may be counterproductive in systems used for the separation of proteins and peptides because they tend to adsorb on highly hydrophobic surfaces. 

It has been possible to fabricate porous monoliths within silicon [16], glass [17], and polymer [18, 19] microchaimels. Within silica and glass channels, porous monoliths can be fabricated by a thermally aided sol-gel reaction. Photopolymerization of acrylate monomers in the presence of porogens (inert organic solvents) has also been used to obtain porous monoliths. By varying the composition of the monomer blend, the composition of the porogen mixture, and the ratio of monomer to porogen, it is possible to control the porosity of the monolith and the modal size of its pores. In addition, if the channels are made out of acrylate... 

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